Antidoting herbicidal 3-isoxazolidinone compounds

ABSTRACT

This invention embodies compositions comprising herbicidally effective compounds corresponding to the formula ##STR1## in which R 1  and R 2  are independently methyl or ethyl, 
     X is H, methyl, chlorine, bromine, fluorine; 
     Y is chlorine, bromine, fluorine; and 
     n is 0, 1 or 2 
     and a non-phytotoxic antidotally effective amount of an antidote therefor selected from the group of amides of haloalkanoic acids, including oxazolidines and thiazolidines, aromatic oxime derivatives, thiazole carboxylic acids and derivatives, substituted phenylpyrimidines, 2-(dichloroacetyl)-2-methyl-1,3-dioxolane and 2-(dichloromethyl)-2-thiazoline.

This is a continuation, of application Ser. No. 07/795,402, filed Nov.26, 1991 (U.S. Pat. No. 5,395,816) which is a continuation-in-part ofapplication Ser. No. 07/652,502, filed Dec. 12, 1990, now abandoned.

FIELD OF THE INVENTION

This invention pertains to herbicidal compositions and methods of useand more particularly to herbicidal compositions comprising3-isoxazolidinone compounds and antidotes therefor which are useful asherbicides.

BACKGROUND OF THE INVENTION

Many herbicides injure crop plants at rates necessary to control weedgrowth. However, to be effective an herbicide must cause minimal damage,preferably no damage, to the beneficial crop while maximizing damage toweed species which infest the locus of the crop.

Herbicides have gained a high degree of commercial success because ithas been shown that such compounds can increase crop yield and reduceharvesting costs. Some of these herbicides include types such astriazines, halogenated acetanilides, carbamates, thiolcarbamates,benzoic acid derivatives, urea derivatives and the like.

In some cases, a crop species may be susceptible to the effects of theherbicide. To preserve protection of crop species from herbicide injuryalong with the concomitant herbicidal effectiveness of weed species, useof chemical compounds called antidotes or safeners have been employed.See, for example, U.S. Pat. Nos. 4,021,224 and 4,230,874.

Although the effects of antidotes against herbicide injury can beestablished under field and greenhouse conditions the physiological andbiochemical mechanisms of action have not been established for allcompounds. Nevertheless, the use of antidote compounds with herbicidesis a widely accepted agronomic practice. These compounds are used oncrops including agronomic and vegetable species.

The isoxazolidinone compounds have been found to be very effectiveherbicides with broad general herbicidal activity against a wide varietyof plant species. Many active 3-isoxazolidinone herbicidal compounds aredisclosed in U.S. Pat. No. 4,405,357 which is incorporated herein in itsentirety by reference. The method of controlling vegetation with thecompounds comprises applying an herbicidally effective amount of theisoxazolidinone, usually with an inert carrier, to the area whereherbicidal control is desired.

The isoxazolidinone compounds have been found in some instances toadversely affect or interfere with the culture of a variety of crops. Inparticular, gramineous crops such as corn are sensitive to theapplication of effective weed controlling rates. Therefore, theeffective use of these herbicides for controlling weeds in the presenceof such crops is further enhanced by, or may require in many instances,the addition of an antidotally effective amount of a compound, which isantidotally effective with the isoxazolidinone herbicide.

It is the objective of this invention to increase the spectrum of cropplants in which an active herbicidal 3-isoxazolidinone compound may beused without injury to the crop and without decreasing the herbicidalefficacy against weeds.

SUMMARY OF THE INVENTION

This invention comprises novel herbicidal compositions which provideexcellent protection for a variety of crops from adverse herbicidalinjury which composition comprises an herbicidally effective amount of a3-isoxazolidinone and a substantially non-phytotoxic,antidotally-effective amount of an herbicide antidote, selected from thegroup consisting of amides of haloalkanoic acids, aromatic oximederivatives, thiazole carboxylic acids and derivatives and substitutedphenylpyrimidines.

In a preferred embodiment the composition also includes a second orco-herbicide preferably a thiolcarbamate, in particular S-ethyl dipropylthiolcarbamate.

The invention also comprises a method for controlling undesirablevegetation in the presence of a crop, particularly corn, by applying tothe locus of the crop or undesired vegetation an herbicidal compositionas described hereinabove.

DETAILED DESCRIPTION OF THE INVENTION

Herbicidal 3-isoxazolidinones are described in U.S. Pat. No. 4,405,357issued Sep. 30, 1983, along with methods for their preparation.

An especially preferred compound is 2-[2-chlorophenyl] methyl-4,4dimethyl-3-isoxazolidinone, example 16 of the above-identified Patent.This compound, COMMAND® is a commercially available herbicide known bythe generic name clomazone. Clomazone is phytotoxic to certain cropswhen applied at rates effective to control undesired vegetation.

One method for production of COMMAND® is disclosed in U.S. Pat. No.4,405,357. Such preparation includes adding to a stirred solution of 6.3grams (0.023 mole) of3-chloro-N-(2-chlorophenyl)methyl-N-hydroxy-2,2-dimethylpropanamide in45 ml of methanol dropwise a solution of 1.5 grams (0.023 mole) KOH (85%pure) in 25 ml methanol. The addition required 15 minutes and thetemperature rose from 24° to 32° C. Upon completion of addition thereaction mixture was stirred for 18 hours at ambient temperature.By-product KCl was removed by filtering the mixture. The filtrate waspoured into 500 ml of ice-water. The mixture was extracted with twoportions of 250 ml each of methylene chloride. The combined extractswere dried with MgSO₄ and filtered. Under reduced pressure the filtratewas concentrated to give 5.2 grams of2-(2-chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone as an

Other substituted 4,4-dimethyl-3-isoxazolidinone herbicidal compoundsmay be prepared in the manner described hereinabove, by varying thereactant compound and amount and the grams of KOH in each case. Forexample, 2-(2-bromophenyl) methyl-4,4-dimethyl-3-isoxazolidinone can beprepared by usingN-(2-bromophenyl)methyl-3-chloro-N-hydroxy-2,2-dimethyl propanamide and0.75 g of 85% pure KOH in 40 ml of methanol.

The active 3-isoxazolidinones of this invention will generally beapplied in diluted form for preemergence or preplant incorporation foreffective control of many broadleaved and grassy weed species. Theactive compounds of this invention may be applied from a tank mix withother herbicides.

A wide range of chemical substances have been found to be effective asherbicide antidotes, and the preferred compositions of this inventioninclude any one or more of such antidotes with the activeisoxazolidinone herbicides. The variety of crops on which the abovedescribed herbicides are useful can be significantly broadened by theuse of an antidote to protect one of more crops from injury therefromand render the composition more selective against weeds. Some of themore important types of antidotes are amides of haloalkanoic acids,aromatic oxime derivatives, thiazole carboxylic acids and derivatives,naphthopyranone derivatives and substituted phenylpyrimidines.

Amides of haloalkanoic acids have the generalized formula ##STR2## inwhich R is a mono- or poly-haloalkyl group. The halogens may bevariously chloro, bromo or iodo; chloro is the preferred halogen, andthe preferred group for R in these compounds in general isdichloromethyl, Cl₂ CH--, i.e., the compounds are amides ofdichloroacetic acid. In such compounds the nitrogen is furthersubstituted by at least one other functional group or forms a portion ofa heterocyclic ring, as will be described below.

Antidotes of this type are described in a number of publications such asU.S. Pat. Nos. 4,021,224; 4,256,481; 4,294,764; 4,900,350; EuropeanPatent Application, Publication No. 104,495, International PatentApplication WO 81/406, and British Patent 1,521,540. U.S. Pat. No.4,021,224 contains a broad disclosure of such types of compounds andindicates a great many possibilities for mono- or di-substitution on thenitrogen atom.

One type of antidote disclosed in U.S. Pat. No. 4,021,224 is N,N-diallyldichloroacetamide, ##STR3## which is generally known commercially asR-25788 or dichlormid.

Another class of haloalkanoic acid amides is that in which the nitrogenatom in the foregoing formula is contained in a heterocyclic ring, forinstance an oxazolidine or thiazolidine ring. Preferably R isdichloromethyl, and the preferred compounds have the general formula##STR4## In this formula, X is oxygen or sulfur, and R₁ -R₆ arevariously independently hydrogen, lower alkyl, alkoxyalkyl,alkylthioalkyl, dialkylaminomethyl, methylcarboxyalkyl, loweralkysulfonylmethyl or phenyl, or R₁ and R₂ taken together form analkylene group, preferably a butylene, pentylene or hexylene group,optionally substituted by one or two methyl groups. Compounds of thesetypes are disclosed, for instance, in U.S. Pat. Nos. 4,021,224,4,256,481, 4,900,350, European Patent Application No. 104,495 andInternational Patent Application WO 81/406.

A preferred group of these compounds has the above formula in which X isoxygen or sulfur; R₁ is hydrogen, C₁ -C₆ alkyl or methylcarboxy (C₁ -C₃)alkyl; R₂ is hydrogen or C₁ -C₆ alkyl; or R₁ and R₂ taken together forma butylene, pentylene or hexylene group optionally substituted by one ortwo methyl groups; R₃ is hydrogen, C₁ -C₆ alkyl, C₂ -C₄ alkoxyalkyl,phenyl or di-(C₁ -C₄ alkyl)aminomethyl (in which the alkyl groups may bethe same or different; R₄ is hydrogen or C₁ -C₆ alkyl; and R₅ and R₆ areindependently hydrogen or C₁ -C₆ alkyl (preferably hydrogen).

Representative compounds of this type include (where not specified, thesubstituent is hydrogen):

Oxazolidines (X=oxygen)

2,2-dimethyl-N-dichloroacetyl oxazolidine (R₁ and R₂ =methyl);

2,2-5 trimethyl-N-dichloroacetyl oxazolidine (R₁, R₂ and R₃ =methyl);

2,2-dimethyl-5-n-propyl-N-dichloroacetyl oxazolidine (R₁, R₂ =methyl, R₃=n-propyl);

2,2-spirocyclohexyl-N-propyl-N-dichloroacetyl oxazolidine (R₁ plus R₂taken together=pentamethylene);

2,2-dimethyl-N-dichloroacetyl-5-ethyl oxazolidine (R₁, R₂ =methyl, R₃=ethyl);

2,2-dimethyl-5-phenyl-N-dichloroacetyl oxazolidine (R₁, R₂ =methyl, R₃=phenyl);

2,2-dimethyl-5-(diisobutylaminomethylene)-N-dichloroacetyl oxazolidine(R₁, R₂ =methyl; R₃ =(N,N-diisobutylamino) methylene;

Thiazolidine (X=sulfur)

2-methyl, 2-methylcarboxymethyl-N-dichloroacetyl thiazolidine (R₁=methyl, R₂ =CH₂ COOCH₃);

2,2 dimethyl-N-dichloroacetyl thiazolidine (R₁ and R₂ =methyl)

Other compounds in which R₁ and R₂ taken together are alkylene aredisclosed for instance in British Patents 1,512,540 and 2,023,582 andHungarian Patent 181,621.

A third type of haloalkanoic acid amide is disclosed generally in U.S.Pat. No. 4,294,764 and has the general formula ##STR5## in which R₇ maybe one of a number of alkyl, alkenyl or alkynyl moieties; R₈, R₉, R₁₀and R₁₁ are independently hydrogen or methyl; and n is 0 or 1. Arepresentative compound of this type is the compoundN-(1,3-dioxolan-2-yl-methyl)-N-(2-propenyl)-2,2-dichloroacetamide, whichhas the formula ##STR6## This corresponds to the previous formula inwhich R₇ is 2-propenyl, R₈ and R₉ are both hydrogen and n is 0.

A fourth type of haloalkanoic acid amide is disclosed in U.S. Pat. Nos.4,601,745 and 4,618,361, and has the general formula ##STR7## in which,among others, R₁ is C₁ -C₆ haloalkyl, R₂ -R₅ are independently hydrogenor C₁ -C₄ alkyl, R₆ and R₇ are hydrogen, halogen, and a number of othersubstituents, and X is oxygen, sulfur, --SO-- or --SO₂. Preferably R₁ isdichloromethyl and X is oxygen. A preferred member of this group is4-(dichloroacetyl)-3,4-benzoxazine (R₁ =dichloromethyl; R₂ =methyl; R₃-R₇ =hydrogen; X=oxygen), also known as CGA-154281.

Substituted phenylpyrimidines are disclosed in U.S. Pat. No. 4,493,726and have the general formula ##STR8## in which R is hydrogen or a numberof substituents; n is an integer from 1 to 5; R₁ and R₃ areindependently halogen or a number of substituents and R₂ is hydrogen,halogen, C₁ -C₆ alkyl, C₁ -C₆ haloalkyl or phenyl. One member of thisgroup is 4,6-dichloro,2-phenylpyrimidine (R=hydrogen, R₁ and R₃=chlorine; R₂ =hydrogen), also known as fenchorim or CGA-123407.

Oxime derivatives which are suitable for use as antidotes withherbicides are disclosed, for instance, in U.S. Pat. Nos. 4,070,389 and4,269,775 and have the general formula ##STR9## in which R₁₃ isoptionally hydrogen, methyl, methoxy, chlorine, cyano ortrifluoromethyl, and in which R₁₂ is cyano or a number of other moietiesas indicated in U.S. Pat. No. 4,269,775. Representative compounds ofthis type are those in which R₁₂ is cyano and in which R₁₃ is 1,3dioxolan-2-yl. The latter compound has the chemical nameO-[2-(1,3-dioxolanyl)methyl]-alpha-cyano-benzaldoxime.

Thiazole carboxylic acids and derivatives suitable for use as antidotesare disclosed generally in U.S. Pat. No. 4,199,506 and have the generalformula ##STR10## in which R₁₆ is alkyl, haloalkyl or trialkoxymethyl;R₁₄ is variously hydrogen, agriculturally acceptable cations or varioushydrocarbamyl or substituted hydrocarbamyl moieties; m is 0 or 1 and R₁₅is chloro, bromo, iodo, lower alkoxy or substituted or unsubstitutedphenoxy. A representative member of this class is the compoundbenzyl-2-chloro-4-trifluoromethyl-5-thiazole carboxylate (R₁₆=trifluoromethyl; R₁₄ =benzyl, R₁₅ =chloro; m=1).

Two other antidotes which may be used with the active isoxazolidinoneherbicide in compositions according to this invention are: ##STR11##

The amount of a given antidote to be utilized in combination with theherbicide composition of this invention and the manner of itsutilization and resulting efficacy can vary according to variousparameters such as the particular antidote to be employed, the cropwhich is to be protected, the amount or rate of herbicide to be applied,and the soil and climatic conditions of the agricultural environment inwhich the mixture is to be applied. The selection of a specific antidotefor use in the herbicide composition, the manner in which it is to beapplied (e.g., tank mix, infurrow application, seed treatment, etc.),the determination of activity which is non-phytotoxic but antidotallyeffective, and the amount necessary to provide this result, can bereadily performed utilizing the test procedures in the cited patentssuch as U.S. Pat. No. 4,021,224, in accordance with common practice inthe art.

The antidote is applied in conjunction with the herbicide in anon-phytotoxic antidotally effective amount. "Non-phytotoxic" is definedas an amount of the antidote which causes at most minor or no injury tothe desired crop species. "Antidotally effective" is defined as anantidote used in an amount which is effective as an antidote with theherbicide to decrease the extent of injury caused by the herbicide tothe desired crop species.

"Herbicidally effective" is defined as the amount of herbicide requiredto effect a meaningful injury or destruction of a significant portion ofaffected undesired weeds or plants.

Another embodiment of this invention includes thiolcarbamateco-herbicides in the composition comprising 3-isoxazolidinone compoundsand antidotes thereof. Co-herbicidal compounds of preference include thefollowing:

S-ethyl dipropyl thiolcarbamate

S-ethyl diisobutyl thiolcarbamate

S-propyl dipropyl thiolcarbamate

S-2,3,3-trichloroallyl diisopropyl thiolcarbamate

S-ethyl N-cyclohexyl N-ethylthiolcarbamate

S-ethyl bis-(2-methylpropyl) carbamothioate

All of the above specifically-named herbicides are known in the art, andthey are described in U.S. Pat. Nos. 2,913,327 and 3,330,643.

Still other classes of herbicidal compounds contemplated for combinationwith this invention include acetamide herbicides such as alachlor,butachlor, acetochlor and metolachlor; S-triazine herbicides such asmetribuzin; p-toluidine herbicides such as trifluralin; sulfonylureaherbicides such as nicosulfuron and primisulfuron; benzoic acidderivatives such as dicamba and the like.

In some cases it may be advantageous to also include in the compositiona substance which can provide extension in time of the activity ofthiolcarbamate herbicides, in an amount effective to extend thisactivity. Such substances are generally referred to as "thiolcarbamateherbicide extenders." A number of substances have been found whichpossess these properties. Examples of such substances are certain typesof organophosphorus compounds, carbamates and amines, which aredisclosed respectively in European Patent Applications Publication Nos.10,178, 38,945, and 78,146 and a number of carbamates, thiocarbamatesand dithiocarbamates as disclosed in Canadian Patent No. 1,262,059.These patent applications disclose tests for determining whether asubstance has such extending activity, and determining what amount ofsubstance is required in a given case to provide this activity. As withthe antidotes, such thiocarbamate herbicide extenders may be physicallyincorporated into the herbicidal composition or applied separately tothe same ultimate locus. Preferred extenders in such compositions arethe compound O,O-diethyl-O-phenyl phosphorothioate, disclosed for suchuse in European Patent Application, Publication No. 10,178 andN,N-bis(3-chloroallyl) S-ethyl thiocarbamate, disclosed in the CanadianPatent No. 1,262,059.

The herbicidal compositions according to this invention contain the3-isoxazolidinone and antidotes in a weight ratio, respectively, of fromabout 0.1:1.0 to about 30:1 (exclusive of auxiliary ingredients).Another preferred weight ratio is from about 1:1 to about 20:1. An evenmore preferred weight ratio from about 2:1 to about 15:1.

Biological Evaluation

The following examples are provided for illustrative purposes only andare not intended as necessarily representative of the overall testingperformed and are not intended to limit the invention in any way. As oneskilled in the art is aware, in herbicidal testing, a significant numberof factors that are not readily controllable can affect the results ofindividual tests. Results may vary depending on environmental factors,depth of planting, the application rate of the herbicide and antidote,the ratio of components in an herbicidal composition and the nature ofplants being tested. Additionally results may vary from crop to crop andwithin varieties.

The following antidotes were employed in Example I and in Tables I andII:

1=N,N-diallyl dichloroacetamide

2=2,2,5-trimethyl-N-dichloroacetyl oxazolidine

3=2,2 dimethyl-N-dichloroacetyl thiazolidine

The following hybrids of corn were employed in Example I and in TablesI, II:

A=CN 8415

B=CN 7751

C=CN 6595

D=CN 7780

E=CN 3901

EXAMPLE I

The herbicide COMMAND® and antidotes as described hereinabove wereapplied preemergence onto soil in aluminum flats (10×21×6 cm deep) froma tank mix solution with a carrier volume of 25 gal/A. Seeds wereplanted 2 cm deep, in a sandy loam soil with pH 6.7, 0.8% organic matterand 8.9% clay. The soil was fortified with 17--17--17 fertilizer and thefungicide Captam 80W. Five hybrids of corn were utilized as summarizedhereinabove. Additionally, green foxtail (Setaria viridis) was planted.

After treatment, all flats were placed into a greenhouse Greenhouseswere maintained at about 25° C. and 20° C., day and night temperature,respectively. All flats were watered to field capacity. Visual ratingsof weed control and crop injury were recorded 9 days after treatment(Table I) and 27 days after treatment (Table II) corresponding to earlyrating data and late rating data. Ratings are stated as percentage ofweed control of each weed species as compared with an untreated control.The control ratings range from 0 to 100%, where 0 represents no effecton growth and 100 represents complete kill. Additionally, ratings arestated as percent tolerance for individual corn varieties, where 0represents no effect on a given parameter and 100 represents completeeffect on a given parameter.

Good protection from bleaching and stunting resulted in corn withantidote compounds at the early rating (Table I) with lower rates ofCOMMAND®.

Late ratings (Table II) indicate that corn itself would outgrow thelower level of injury observed at lower COMMAND® application rates,however, the lower rate of injury that appeared in the early ratingsindicate that the antidotes could be used to eliminate the bleachingsymptoms that appear due to carryover, or eliminate unacceptable earlyinjury to corn.

                                      TABLE I                                     __________________________________________________________________________    MEAN PERCENT CORN TOLERANCE AND WEED CONTROL                                  NINE DAYS AFTER TREATMENT                                                     __________________________________________________________________________                         Corn Variety Tolerance                                   Herbicide  Rate  Green                                                                             A   B   C   D   E   AVG                                  & Antidote (lb/A)                                                                              Foxtail                                                                             2 1 2 1 2 1 2 1 2 1 2                                  __________________________________________________________________________    COMMAND ®                                                                            0.03125 +                                                                           65  65                                                                              30                                                                              40                                                                              0 30                                                                              10                                                                              5 5 0 20                                                                              28                                                                              13                                            0                                                                  COMMAND ® + 1                                                                        0.03125 +                                                                           65  20                                                                              15                                                                              5 5 0 0 3 0 0 0 6 4                                             0.25                                                                          0.03125 +                                                                           35  5 0 0 5 0 0 0 10                                                                              0 10                                                                              1 5                                             0.5                                                                           0.03125 +                                                                           55  5 5 0 5 0 0 5 0 0 5 2 3                                             1.0                                                                COMMAND ® + 2                                                                        0.03125 +                                                                           70  10                                                                              5 5 5 3 0 15                                                                              10                                                                              0 10                                                                              7 6                                             0.125                                                                         0.03125 +                                                                           35  0 0 0 0 0 0 0 0 0 5 0 1                                             0.25                                                                          0.03125 +                                                                           65  0 10                                                                              0 10                                                                              0 10                                                                              10                                                                              5 0 10                                                                              2 9                                             0.50                                                               COMMAND ® + 3                                                                        0.03125 +                                                                           40  3 5 15                                                                              10                                                                              3 5 3 5 0 5 5 6                                             0.125                                                                         0.03125 +                                                                           40  0 0 0 0 0 0 0 0 0 5 0 1                                             0.25                                                               __________________________________________________________________________                         Corn Variety Tolerance                                   Herbicide  Rate  Green                                                                             A   B   C   D   E   AVG                                  & Antidote (lb/A)                                                                              Foxtail                                                                           1 2 1 2 1 2 1 2 1 2 1 2                                  __________________________________________________________________________    COMMAND ®                                                                            0.03125 +                                                                           45  0 0 0 5 0 5 0 10                                                                              0 10                                                                              0 6                                             0.50                                                               Control    0 + 0 0   0 5 0 5 0 5 0 5 0 10                                                                              0 6                                  COMMAND ®                                                                            0.0625 +                                                                            70  60                                                                              5 60                                                                              0 40                                                                              5 40                                                                              10                                                                              0 5 40                                                                              5                                             0                                                                  COMMAND ® + 1                                                                        0.0625 +                                                                            75  25                                                                              15                                                                              20                                                                              10                                                                              20                                                                              10                                                                              5 0 0 0 14                                                                              7                                             0.25                                                                          0.0625 +                                                                            40  40                                                                              10                                                                              25                                                                              10                                                                              10                                                                              5 0 5 0 0 15                                                                              6                                             0.5                                                                           0.0625 +                                                                            75  35                                                                              10                                                                              35                                                                              10                                                                              40                                                                              0 35                                                                              10                                                                              5 5 30                                                                              7                                             1.0                                                                COMMAND ® + 2                                                                        0.0625 +                                                                            85  35                                                                              5 30                                                                              0 15                                                                              5 20                                                                              10                                                                              0 10                                                                              20                                                                              6                                             0.125                                                                         0.0625 +                                                                            60  10                                                                              5 5 5 3 10                                                                              3 5 0 5 4 6                                             0.25                                                                          0.0625 +                                                                            95  30                                                                              10                                                                              30                                                                              5 10                                                                              5 10                                                                              5 0 10                                                                              16                                                                              7                                             0.5                                                                COMMAND ® + 3                                                                        0.0625 +                                                                            95  15                                                                              5 15                                                                              10                                                                              5 15                                                                              25                                                                              5 5 15                                                                              13                                                                              10                                            0.125                                                                         0.0625 +                                                                            75  10                                                                              5 0 5 0 0 3 0 0 5 3 3                                             0.25                                                                          0.0625 +                                                                            85  10                                                                              5 0 10                                                                              3 10                                                                              5 5 0 10                                                                              4 8                                             0.50                                                               Control    0 + 0 0   0 0 0 0 0 10                                                                              0 10                                                                              0 5 0 5                                  COMMAND ®                                                                            0.125 +                                                                             95  85                                                                              10                                                                              75                                                                              35                                                                              70                                                                              10                                                                              70                                                                              5 20                                                                              0 64                                                                              12                                            0                                                                  COMMAND ® + 1                                                                        0.125 +                                                                             95  75                                                                              15                                                                              65                                                                              15                                                                              60                                                                              10                                                                              75                                                                              10                                                                              5 10                                                                              56                                                                              12                                            0.25                                                                          0.125 +                                                                             95  40                                                                              15                                                                              35                                                                              5 25                                                                              10                                                                              40                                                                              0 0 5 28                                                                              7                                             0.5                                                                           0.125 +                                                                             95  85                                                                              30                                                                              60                                                                              15                                                                              50                                                                              0 70                                                                              0 0 10                                                                              53                                                                              11                                            1.0                                                                COMMAND ® + 2                                                                        0.125 +                                                                             95  60                                                                              15                                                                              60                                                                              10                                                                              40                                                                              5 40                                                                              10                                                                              5 10                                                                              41                                                                              10                                            0.125                                                                         0.125 +                                                                             95  40                                                                              0 35                                                                              0 30                                                                              5 40                                                                              15                                                                              3 5 30                                                                              5                                             0.25                                                                          0.125 +                                                                             100 60                                                                              15                                                                              50                                                                              10                                                                              40                                                                              10                                                                              70                                                                              5 35                                                                              5 51                                                                              9                                             0.50                                                               COMMAND ® + 3                                                                        0.125 +                                                                             98  50                                                                              5 70                                                                              0 60                                                                              0 75                                                                              0 5 0 52                                                                              1                                             0.125                                                                         0.125 +                                                                             95  35                                                                              20                                                                              30                                                                              15                                                                              25                                                                              5 15                                                                              0 0 5 21                                                                              9                                             0.25                                                                          0.125 +                                                                             95  40                                                                              10                                                                              40                                                                              10                                                                              15                                                                              10                                                                              20                                                                              10                                                                              0 10                                                                              23                                                                              10                                            0.50                                                               Control    0 + 0 0   0 15                                                                              0 0 0 5 0 5 0 0 0 5                                  COMMAND ®                                                                            0.25 +                                                                              95  75                                                                              10                                                                              75                                                                              10                                                                              65                                                                              5 75                                                                              5 70                                                                              5 72                                                                              7                                             0                                                                  COMMAND ® + 1                                                                        0.25 +                                                                              100 90                                                                              10                                                                              80                                                                              5 75                                                                              5 80                                                                              10                                                                              60                                                                              10                                                                              77                                                                              8                                             0.25                                                                          0.25 +                                                                              100 75                                                                              10                                                                              75                                                                              15                                                                              65                                                                              10                                                                              75                                                                              15                                                                              35                                                                              10                                                                              65                                                                              12                                            0.05                                                                          0.25+ 100 80                                                                              10                                                                              80                                                                              15                                                                              70                                                                              10                                                                              75                                                                              10                                                                              50                                                                              5 71                                                                              10                                            1.0                                                                COMMAND ® + 2                                                                        0.25 +                                                                              100 80                                                                              10                                                                              80                                                                              10                                                                              75                                                                              10                                                                              85                                                                              15                                                                              40                                                                              0 72                                                                              9                                             0.125                                                                         0.25 +                                                                              100 70                                                                              10                                                                              70                                                                              10                                                                              75                                                                              10                                                                              75                                                                              10                                                                              3 10                                                                              59                                                                              10                                            0.25                                                                          0.25 +                                                                              100 75                                                                              15                                                                              75                                                                              15                                                                              60                                                                              15                                                                              75                                                                              15                                                                              40                                                                              15                                                                              65                                                                              15                                            0.50                                                               COMMAND ® + 3                                                                        0.25 +                                                                              100 75                                                                              15                                                                              75                                                                              10                                                                              65                                                                              10                                                                              85                                                                              15                                                                              65                                                                              0 73                                                                              10                                            0.125                                                                         0.25 +                                                                              95  50                                                                              10                                                                              25                                                                              5 25                                                                              5 50                                                                              5 5 5 31                                                                              6                                             0.25                                                                          0.25 +                                                                              100 60                                                                              15                                                                              40                                                                              15                                                                              40                                                                              20                                                                              50                                                                              5 15                                                                              5 41                                                                              12                                            0.50                                                               Control    0 + 0 0   0 0 0 10                                                                              0 5 0 5 0 5 0 5                                  __________________________________________________________________________     COMMAND ®, 2(2-chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone         1 = Pigment loss (incidence of bleaching and chlorosis)                       2 = Stunting                                                             

                                      TABLE II                                    __________________________________________________________________________    MEAN PERCENT CORN TOLERANCE AND WEED CONTROL                                  27 DAYS AFTER TREATMENT                                                                            Corn Variety Tolerance                                   Herbicide  Rate  Green                                                                             A     B   C   D   E   AVG                                & Antidote (lb/A)                                                                              Foxtail                                                                           1  2  1 2 1 2 1 2 1 2 1 2                                __________________________________________________________________________    COMMAND ®                                                                            0.03125 +                                                                           25  5  0  0 0 0 0 0 0 0 0 1 0                                           0                                                                  COMMAND ® + 1                                                                        0.03125 +                                                                           25  0  0  0 0 0 0 0 0 0 0 0 0                                           0.25                                                                          0.03125 +                                                                           0   0  0  0 0 0 0 0 0 0 0 0 0                                           0.50                                                                          0.03125 +                                                                           40  0  0  0 0 0 0 0 0 0 0 0 0                                           01.0                                                               COMMAND ® + 2                                                                        0.03125 +                                                                           25  0  0  0 0 0 0 0 0 0 0 0 0                                           0.125                                                                         0.03125 +                                                                           10  0  0  0 0 0 0 0 0 0 0 0 0                                           0.25                                                                          0.03125 +                                                                           35  0  0  0 0 0 0 0 0 0 0 0 0                                           0.50                                                               COMMAND ® + 3                                                                        0.03125 +                                                                           0   0  0  0 0 0 0 0 0 0 0 0 0                                           0.125                                                                         0.03125 +                                                                           0   0  0  0 0 0 0 0 0 0 0 0 0                                           0.25                                                                          0.03125 +                                                                           10  0  0  0 0 0 0 0 0 0 0 0 0                                           0.50                                                               Control    0 + 0 0   0  0  0 0 0 0 0 0 0 0 0 0                                COMMAND ®                                                                            0.0625 +                                                                            20  5  5  5 0 10                                                                              0 5 15                                                                              0 0 5 4                                COMMAND ® + 1                                                                        0.0625 +                                                                            15  5  0  5 20                                                                              0 15                                                                              5 0 5 15                                                                              4 10                                          0.25                                                                          0.0625 +                                                                            0   0  0  0 0 0 0 0 0 0 0 0 0                                           0.50                                                                          0.0625 +                                                                            20  20 15 5 0 20                                                                              0 20                                                                              0 5 0 14                                                                              3                                           1.0                                                                COMMAND ®  + 2                                                                       0.0625 +                                                                            65  10 0  5 0 5 0 10                                                                              0 0 0 6 0                                           0.125                                                                         0.0625 +                                                                            10  0  0  0 0 0 0 0 0 0 0 0 0                                           0.25                                                                          0.0625 +                                                                            80  15 10 5 0 5 0 10                                                                              5 5 0 7 2                                           0.5                                                                COMMAND ® + 3                                                                        0.0625 +                                                                            30  5  0  5 0 3 0 10                                                                              5 5 0 6 1                                           0.125                                                                         0.0625 +                                                                            35  3  0  0 0 0 0 5 0 0 0 2 0                                           0.25                                                                          0.0625 +                                                                            35  10 5  0 0 0 0 10                                                                              0 0 0 4 1                                           0.50                                                               Control    0 + 0 0   0  0  0 0 0 0 0 0 0 0 0 0                                COMMAND ®                                                                            0.125 +                                                                             90  50 70 20                                                                              10                                                                              5 20                                                                              20                                                                              30                                                                              10                                                                              0 21                                                                              26                                          0                                                                  COMMAND ® + 1                                                                        0.125 +                                                                             85  35 25 30                                                                              0 10                                                                              0 10                                                                              20                                                                              5 0 18                                                                              9                                           0.25                                                                          0.125 +                                                                             60  15 5  10                                                                              0 5 0 20                                                                              0 20                                                                              0 14                                                                              1                                           0.50                                                                          0.125 +                                                                             80  50 75 40                                                                              20                                                                              40                                                                              20                                                                              40                                                                              20                                                                              35                                                                              0 41                                                                              27                                          1.0                                                                COMMAND ® + 2                                                                        0.125 +                                                                             90  10 0  30                                                                              0 5 5 20                                                                              10                                                                              15                                                                              0 15                                                                              3                                           0.125                                                                         0.125 +                                                                             50  10 0  15                                                                              5 10                                                                              0 30                                                                              15                                                                              15                                                                              0 16                                                                              4                                           0.25                                                                          0.125 +                                                                             95  40 15 40                                                                              0 40                                                                              0 70                                                                              40                                                                              35                                                                              10                                                                              45                                                                              13                                          0.50                                                               COMMAND ® + 3                                                                        0.125 +                                                                             95  30 5  20                                                                              0 15                                                                              0 40                                                                              35                                                                              20                                                                              0 25                                                                              8                                           0.125                                                                         0.125 +                                                                             100 15 15 10                                                                              10                                                                              15                                                                              5 25                                                                              0 15                                                                              0 15                                                                              4                                           0.25                                                                          0.125 +                                                                             100 35 0  25                                                                              10                                                                              15                                                                              10                                                                              35                                                                              0 20                                                                              0 25                                                                              4                                           0.50                                                               Control    0 + 0 0   0  0  0 0 0 0 0 0 0 0 0 0                                COMMAND ®                                                                            0.25 +                                                                              100 75 50 70                                                                              40                                                                              65                                                                              35                                                                              50                                                                              50                                                                              50                                                                              35                                                                              62                                                                              42                                          0                                                                  COMMAND ® + 1                                                                        0.25 +                                                                              100 100                                                                              100                                                                              75                                                                              50                                                                              70                                                                              40                                                                              75                                                                              75                                                                              50                                                                              0 74                                                                              53                                          0.25                                                                          0.25 +                                                                              100 25 80 65                                                                              40                                                                              50                                                                              30                                                                              50                                                                              20                                                                              40                                                                              20                                                                              46                                                                              38                                          0.50                                                                          0.25 +                                                                              100 100                                                                              100                                                                              85                                                                              75                                                                              65                                                                              40                                                                              65                                                                              40                                                                              65                                                                              35                                                                              76                                                                              58                                          1.0                                                                COMMAND ® + 2                                                                        0.25 +                                                                              100 100                                                                              100                                                                              75                                                                              45                                                                              70                                                                              30                                                                              75                                                                              50                                                                              40                                                                              5 72                                                                              46                                          0.125                                                                         0.25 +                                                                              100 35 60 35                                                                              20                                                                              25                                                                              20                                                                              50                                                                              40                                                                              20                                                                              0 33                                                                              28                                          0.25                                                                          0.25 +                                                                              100 75 75 75                                                                              50                                                                              50                                                                              50                                                                              75                                                                              40                                                                              70                                                                              45                                                                              69                                                                              52                                          0.50                                                               COMMAND ® + 3                                                                        0.25 +                                                                              100 100                                                                              100                                                                              75                                                                              35                                                                              75                                                                              50                                                                              75                                                                              75                                                                              35                                                                              50                                                                              72                                                                              62                                          0.125                                                                         0.25 +                                                                              90  35 35 35                                                                              35                                                                              30                                                                              25                                                                              35                                                                              30                                                                              35                                                                              30                                                                              34                                                                              31                                          0.25                                                                          0.25 +                                                                              98  75 70 75                                                                              40                                                                              40                                                                              20                                                                              60                                                                              20                                                                              40                                                                              25                                                                              58                                                                              35                                          0.50                                                               Control    0 + 0 0   0  0  0 0 0 0 0 0 0 0 0 0                                __________________________________________________________________________     1 = Pigment loss (incidence of bleaching and chlorosis)                       2 = Stunting                                                                  A. COMMAND ® 2(2-chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone  

EXAMPLE 2

The experimental conditions were as described in Example 1. However,both COMMAND® and ERADICANE® were applied to sandy loam soil bypre-plant incorporation 3 inch deep. Seeds of giant foxtail and two cornhybrids were planted, 2 cm deep in aluminum flats.

An objective of this test was to determine if additional amounts ofCompound 2 would be required to antidote COMMAND® injury. ERADICANE®contains a 24:1 ratio of ERADICANE® to Compound 2; additional mixtureswere made to contain a 12:1 and 6:1 ratio of ERADICANE® to Compound 2.These mixtures were applied pre-plant incorporation to 1.0, 1.5, 2.0 and3.0 oz/A COMMAND®. The results are exhibited in Table III.

                  TABLE III                                                       ______________________________________                                        ANTIDOTING OF COMMAND INJURY BY                                               ERADICANE 11 DAYS AFTER TREATMENT                                                                       % Corn                                              Herbicide.sup.1                                                                             Rate        Variety Tolerance.sup.3                             Treatment     (oz/A + lb/A)                                                                             GF.sup.2                                                                              A    B.sup.4                                ______________________________________                                        COMMAND ® 1.0 + 0     82      37.0 30.0                                   COMMAND ® +                                                                             1.0 + 4.0   99      2.0  7.0                                    ERADICANE ®                                                               COMMAND ® +                                                                             1.0 + 4.0   83      0.0  3.0                                    ERADICANE ® 2X                                                            COMMAND ® +                                                                             1.0 + 4.0   96      0.0  7.0                                    ERADICANE ® 4X                                                            COMMAND ® 1.5 + 0     75      43.0 47.0                                   COMMAND ® +                                                                             1.5 + 4.0   98      7.0  17.0                                   ERADICANE ®                                                               COMMAND ® +                                                                             1.5 + 4.0   88      8.0  10.0                                   ERADICANE ® 2X                                                            COMMAND ® 1.5 + 4.0   98      5.0  12.0                                   ERADICANE ® 4X                                                            COMMAND ® 2.0 + 0     92      63.0 60.0                                   COMMAND ® +                                                                             2.0 + 4.0   95      20.0 18.0                                   ERADICANE ®                                                               COMMAND ® +                                                                             2.0 + 4.0   95      22.0 23.0                                   ERADICANE  ® 2X                                                           COMMAND ® +                                                                             2.0 + 4.0   100     22.0 25.0                                   ERADICANE ® 4X                                                            COMMAND ® 3.0 + 0     98      78.0 75.0                                   COMMAND ® +                                                                             3.0 + 4.0   95      60.0 63.0                                   ERADICANE ®                                                               COMMAND ® +                                                                             3.0 + 4.0   99      37.0 45.0                                   ERADICANE ® 2X                                                            COMMAND ® +                                                                             3.0 + 4.0   100     30.0 38.0                                   ERADICANE ® 4X                                                            ______________________________________                                         .sup.1 COMMAND ® = 2  (2chlorophenyl)methyl-4,4                           dimethyl3-isoxazolidinone                                                     ERADICANE ® = Sethyl-N,N, dipropylthiocarbamate (EPTC) plus               2,2,5trimethyl 3(dichloroacetyl)-1,3-oxazolidine (Compound 2)                 ERADICANE ® contains a 24:1 ratio of EPTC to Compound 2,                  ERADICANE ® 2X contains a 12:1 ratio of EPTC to Compound 2                ERADICANE ® 4X contains a 6:1 ratio of EPTC to Compound 2                 .sup.2 GF = Giant Foxtail at 28 DAT                                           .sup.3 Mean % pigment loss                                                    .sup.4 A = CN 656                                                             B = CN 8711                                                              

ERADICANE® reduced COMMAND® injury on both corn hybrids. Increasing theratio of antidote compound No. 2 did not further reduce corn injury withrates of COMMAND® between 1-2 oz/A. When 3.0 oz/A COMMAND® was appliedsevere corn injury was observed. Additional antidote applied withERADICANE® (2× and 4× treatments) antidoted COMMAND® injurysignificantly better than ERADICANE® alone.

EXAMPLE 3

Field experiments were conducted using a randomized block design withthree replications per treatment. COMMAND® or COMMAND® and ERADICANE®6.7-E formulated as an emulsifable concentrate were tank mixed andpre-plant incorporated into the soil. ERADICANE® 6.7-E was applied atthe rate of 4 lb/A. COMMAND® was applied at the rate of 0.062, 0.125,0.250 and 0.375 lb/A. Field corn, P3475, a moderately tolerant hybrid toCOMMAND® injury and P3377, a susceptible hybrid to COMMAND® injury wereseeded on the same day as treatment. Corn injury and weed control wereevaluated 10 and 27 days after treatment (Tables IV and V) ashereinabove discussed.

The percent chlorosis exhibited in both corn hybrids at 10 and 27 daysafter treatment increased with increased application rates of COMMAND®.When ERADICANE® was applied the percent chlorosis of both corn hybridssignificantly decreased at the higher rates of COMMAND® application.

                                      TABLE IV                                    __________________________________________________________________________    MEAN PERCENT CORN INJURY AND WEED CONTROL                                     TEN DAYS AFTER TREATMENT                                                      Herbicide.sup.1                                                                          Rate                                                                              Giant                                                                             Velvet                                                                            Redroot                                                                            Corn Variety Injury.sup.2                         Treatment  (lb/A)                                                                            Foxtail                                                                           Leaf                                                                              Pigweed                                                                            A    B.sup.3                                      __________________________________________________________________________    ERADICANE ®                                                                          4.0 90  100 100  0    0                                            ERADICANE ® +                                                                        4.0 +                                                                             98  100 100  13   10                                           COMMAND ®                                                                            0.062                                                              ERADICANE ® +                                                                        4.0 +                                                                             100 100 100  15   2                                            COMMAND ®                                                                            0.125                                                              ERADICANE ® +                                                                        4.0 +                                                                             100 100 100  63   30                                           COMMAND ®                                                                            0.25                                                               ERADICANE ® +                                                                        4.0 +                                                                             100 100 100  73                                                COMMAND ®                                                                            0.375                                                              COMMAND ®                                                                            0.062                                                                             22  55  42   18   8                                            COMMAND ®                                                                            0.125                                                                             38  32  52   63   23                                           COMMAND ®                                                                            0.25                                                                              65  93  77   78   63                                           COMMAND ®                                                                            0.375                                                                             88  97  97   90   78                                           Control        0   0   0    2    0                                            __________________________________________________________________________     .sup.1 ERADICANE ® = EPTC (Sethyl-dipropylthiocarbamate) plus antidot     Compound No. 2 (2,2 5trimethyl-3-(dichloroacetyl)-1,3 oxazolidine)            COMMAND ® =  2(2-chlorophenyl)methyl-4,4-dimethyl-3-isoazoladinone        .sup.2 % clorosis                                                             .sup.3 A = Zea mays P3377 (susceptible hybrid to COMMAND ® injury)        B = Zea mays P3475 (moderately tolerant hybrid to COMMAND ® injury)  

                                      TABLE V                                     __________________________________________________________________________    MEAN PERCENT CORN INJURY AND WEED CONTROL                                     27 DAYS AFTER TREATMENT                                                       Herbicide.sup.1                                                                          Rate                                                                              Giant                                                                             Velvet                                                                            Redroot                                                                            Corn Variety Injury.sup.2                         Treatment  (lb/A)                                                                            Foxtail                                                                           Leaf                                                                              Pigweed                                                                            A    B.sup.3                                      __________________________________________________________________________    ERADICANE ®                                                                          4.0 100 100 100  0    0                                            ERADICANE ® +                                                                        4.0 +                                                                             100 100 100  4    2                                            COMMAND ®                                                                            0.062                                                              ERADICANE ® +                                                                        4.0 +                                                                             100 100 100  17   3                                            COMMAND ®                                                                            0.125                                                              ERADICANE ® +                                                                        4.0 +                                                                             100 100 100  30   12                                           COMMAND ®                                                                            0.25                                                               ERADICANE ® +                                                                        4.0 +                                                                             100 100 100  40   30                                           COMMAND ®                                                                            0.375                                                              COMMAND ®                                                                            0.062                                                                             13  82  98   3    1                                            COMMAND ®                                                                            0.125                                                                             67  100 100  21   11                                           COMMAND ®                                                                            0.25                                                                              67  100 100  38   27                                           COMMAND ®                                                                            0.375                                                                             97  100 100  78   66                                           Control        0   0   0    2    0                                            __________________________________________________________________________     .sup.1 ERADICANE ® = EPTC (Sethyl-dipropylthiocarbamate) plus antidot     Compound No. 2 (2,2,5trimethyl-3-(dichloroacetyl)-1,3 oxazolidine)            COMMAND ® =  2(2-chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone       .sup.2 % clorosis                                                             .sup.3 A = Zea mays P3377 (susceptible hybrid to COMMAND ® injury         B = Zea mays P3475 (moderately tolerant hybrid to COMMAND ® injury)  

EXAMPLE 4

Field experiments were conducted using a randomized block design withthree replications per treatment. COMMAND® as an emulsifiableconcentrate was sprayed and incorporated to 3 inches in the soil with orwithout the oxazolidine antidote. Each field plot was 6.6 feet by 20feet. Plots were planted to corn and wheat. Two days after planting theplots were irrigated with water due to, dry conditions. Thereafter, nosupplemental irrigation was necessary. The crops were rated for %phytotoxicity (as % bleaching) at 8, 14 and 21 days after treatment. Theresults are exhibited in Table VI.

Injury from the high rate of COMMAND® (0.25 lb/A) was decreased with theantidote. The low rate of COMMAND® (0.125 lb/A) did not causesignificant phytotoxicity and the antidote did not significantly reducethe small % of phytotoxicity. Wheat was not antidoted against COMMAND®at the rates applied.

                                      TABLE VI                                    __________________________________________________________________________    MEAN PERCENT CROP INJURY.sup.1                                                              Corn DK656                                                                           Corn - Pioneer 3165                                                                     Wheat - Saluda                                           Rate                                                                              Days After Treatment                                            Treatment.sup.2                                                                         (lb/A)                                                                            8 14 21                                                                              8  14  21 8  14                                                                              21                                        __________________________________________________________________________    COMMAND ®                                                                           0.125                                                                             8 4  3 7  7   3  17 12                                                                              5                                         COMMAND ® +                                                                         0.125                                                                             2 0  1 2  0   1  17 25                                                                              18                                        Antidote  0.167                                                               COMMAND ®                                                                           0.25                                                                              43                                                                              23 17                                                                              18 23  17 53 38                                                                              32                                        COMMAND ® +                                                                         0.25                                                                              10                                                                              3  7 2  3   7  57 53                                                                              47                                        Antidote  0.167                                                               Antidote  0.167                                                                             3 0  3 3  0   3  0  2 0                                         Control   0   0 0  2 0  0   2  0  0 0                                         __________________________________________________________________________     .sup.1 = % Bleaching                                                          .sup.2 = COMMANDO ® is                                                    2(2-chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone                        Antidote is 2,2,5trimethyl-3-(dichloroacetyl)-1,3-oxazolidine            

The antidote compounds and compositions of the present invention can beused in any convenient form. Thus the antidote compounds can beformulated into emulsifiable liquids, emulsifiable concentrates,liquids, wettable powders, powders, granules, microcapsules, or anyother convenient form. In its preferred form, an herbicidal antidotecompound in a non-phytotoxic quantity with respect to the crop isadmixed with a selected herbicide and incorporated into the soil priorto or after planting the seed or applied pre-emergence. It is to beunderstood, however, that the herbicides can be incorporated into thesoil and thereafter the antidote compound can be incorporated into thesoil. Moreover, the crop seed itself can be treated with anon-phytotoxic quantity of the compound and planted into the soil whichhas been treated with herbicides, or untreated with the herbicide andsubsequently treated with the herbicide. The addition of the antidotecompound does not effect the herbicidal activity of the herbicidesexcept to render the activity selective with respect to beneficialcrops.

The amount of antidote compound present can range between about 0.01 toabout 30 parts by weight of antidote compound described herein per eachpart by weight of herbicide. The exact amount of antidote compound willusually be determined on economic ratios for the most effective amountusable. It is understood that a non-phytotoxic quantity of antidotecompound with respect to a particular crop will be employed in theherbicidal compositions described herein.

FORMULATIONS

The compounds and compositions can be formulated in the same manner inwhich herbicides are generally formulated. The object of the formulationis to apply the compounds and compositions to the locus where control isdesired by conventional method. The locus may include soil, seeds,seedlings, crop, crop seeds and vegetation.

Useful formulations of the compounds of this invention can be preparedin conventional ways. They include dusts, granules, microcapsules,pellets, solutions, suspensions, emulsions, wettable powders,emulsifiable concentrates and the like. Many of these may be applieddirectly to the locus. Sprayable formulations can be extended insuitable media and used at spray volumes of from a few liters to severalhundred liters per hectare. High strength compositions are primarilyused as intermediates for further formulation. The formulations,broadly, contain about 0.1% to 99% by weight of active herbicide andantidote ingredient(s) and optionally at least one of (a) about 0.1% to20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inertdiluent(s). More specifically, they can contain these ingredients in thefollowing approximate proportions.

                  TABLE VII                                                       ______________________________________                                                   Active                                                                        Herb. & Ant.                                                                           Weight Percent*                                                      Ingredients                                                                            Diluent(s)                                                                              Surfactant(s)                                   ______________________________________                                        Wettable Powders                                                                           20-90      0-74      1-10                                        Oil Suspensions                                                                            3-50       40-95     0-15                                        Emulsions, Solutions                                                          (Including                                                                    Emulsifiable                                                                  Concentrates)                                                                 Aqueous Suspension                                                                         10-50      40-84     1-20                                        Dusts        1-25       70-99     1-20                                        Granules and Pellets                                                                       0.1-95     5-99.9    0-15                                        Compositions 90-99      0-10      0-2                                         ______________________________________                                         *Active ingredient plus as least one of a Surfactant or a Diluent equals      100 weight percent.                                                      

Lower or higher levels of active ingredient can be present depending onthe intended use and the physical properties of the compound. Higherratios of surfactant to active ingredient are sometimes desirable, andare achieved by incorporation into the formulation or by tank mixing.

Dusts are free-flowing powder compositions containing the formulantimpregnated on a particulate carrier. The particle size of the carriersis usually in the approximate range of 30 to 50 microns. Examples ofsuitable carriers are talc, bentonite, diatomaceous earth, andpyrophyllite. The composition generally contains up to 50% of formulant.Anti-caking and anti-static agents may also be added. Dusts may beapplied by spraying from boom sprayers, hand sprayers or airplanes.

Wettable powders are finely divided compositions comprising a particularcarrier impregnated with the formulant and additionally containing oneor more surface active agents. The surface active agent promotes rapiddispersion of the powder in an aqueous medium to form stable, sprayablesuspensions. A wide variety of surface active agents can be used, forexample, long chain fatty alcohols and alkali metal salts of sulfatedfatty alcohols; salts of sulfonic acid; esters of long chain fattyacids; and polyhydric alcohols, in which the alcohol groups are free,omega-substituted polyethylene glycols of relatively long chain length.A list of surface active agents suitable for use in agricultureformulations can be found in Wade Van Valkenburg, Pesticide Formulations(Marcel Dekker, Inc., New York, 1973) at pages 79-84.

Granules comprise the formulant impregnated on a particulate inertcarrier having a particle size of about 1 to 2 millimeters (mm) indiameter. The granules can be made by spraying a solution of theformulant in a volatile solvent onto the granular carrier. Examples ofsuitable carriers for the preparation of granules include clay,vermiculate sawdust, and granular carbon.

Microcapsules and other slow release formulations are advantageous asformulations to deliver and distribute the active ingredients.Microcapsules consist of fully enclosed droplets or granules containingthe active materials in which the enclosing material is an inert porousmembrane, arranged to allow escape of the enclosed materials to thesurrounding medium at controlled rates over a specified period of time.Encapsulated droplets are typically about 1 to 50 microns in diameter.The enclosed liquid typically constitutes about 50 to 95% of the weightof the entire capsule, and may contain an amount of solvent in additionto the active materials. Encapsulated granules are characterized byporous membranes sealing the openings of the granule carrier pores,trapping the liquid containing the active components inside forcontrolled release. A typical granule size ranges from 1 millimeter to 1centimeter in diameter. In agricultural usage, the granule size isgenerally about 1 to 2 millimeters in diameter. Granules formed byextrusion, agglomeration or prilling are useful in the present inventionas well as materials in their naturally occurring form. Examples of suchcarriers are vermiculite, starch sintered clay granules, kaolin,attapulgite clay, sawdust and granular carbon. Useful encapsulatingmaterials include natural and synthetic rubbers, cellulosic materials,styrenebutadiene copolymers, polyacrylonitriles, polyacrylates,polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Emulsifiable concentrates consist of an oil solution of the formulantplus and emulsifying agent. Prior to use, the concentrate is dilutedwith water to form a suspended emulsion of oil droplets. The emulsifiersused are usually a mixture of anionic and nonionic surfactants. Otheradditives, such as suspending agents and thickeners, may be included inthe emulsifiable concentrate.

When the formulant is an antidote and herbicide composition, theproportion of antidote compound to herbicide compound generally rangesfrom approximately 0.001 to 30 parts by weight of the antidote compoundper weight of the herbicide compound.

Formulations generally contain several additives in addition to theformulant and carrier or agent. Among these are inert ingredients,diluent carriers, organic solvents, water, oil and water, water in oilemulsions, carriers of dust and granules, and surface active wetting,dispersing and emulsifying agents. Fertilizers, e.g., ammonium nitrateurea and superphosphate, may also be included. Aids to rooting andgrowth, e.g., compost, manure, humus and sand, may also be included.

Alternatively, the compounds and compositions of this invention can beapplied to a crop by addition to irrigation water supplied to the fieldto be treated. This method of application permits the penetration of thecompositions into the soil as the water is absorbed therein.

As another alternative, the formulation can be applied to the soil inthe form of a solution in a suitable solvent. Solvents frequently usedin these formulations include kerosene, fuel oil, xylene, petroleumfractions with boiling ranges above xylene and aromatic petroleumfractions rich in methylated naphthalenes. Liquid solutions, like dusts,may be applied by spraying from boom and hand sprayers or airplanes.

It is claimed:
 1. An herbicidal composition comprising:a) anherbicidally effective amount of a 3-isoxazolidinone herbicide havingthe formula ##STR12## in which R₁ and R₂ are independently methyl orethyl; X is hydrogen, methyl, chlorine, bromine or fluorine; Y ischlorine, bromine or fluorine; and n is 0, 1 or 2; and b) anon-phytotoxic, antidotally effective amount, with respect to a corncrop, of an antidote compound selected from the group consisting ofN-diallyldichloroacetamide and compounds having the formula ##STR13## inwhich X is O or S and R₁ -R₆ are variously independently hydrogen, loweralkyl, alkoxyalkyl, alkylthioalkyl, or phenyl, or R₁ and R₂ takentogether form an alkylene group, and c) a herbicidally effective amountof one or more co-herbicides selected from acetamide herbicides,S-triazine herbicides, p-toluidine, herbicides, and sulfonylureaherbicides.
 2. An herbicidal composition according to claim 1 wherein(c) is an S-triazine herbicide.
 3. An herbicidal composition accordingto claim 1 wherein (c) is an acetamide herbicide.
 4. An herbicidalcomposition according to claim 1 wherein the acetamide herbicide ismetolachlor.
 5. An herbicidal composition according to claim 1 whereinthe acetamide herbicide is alachlor.
 6. An herbicidal compositionaccording to claim 1 wherein the acetamide herbicide is acetochlor. 7.An herbicidal composition according to claim 1 wherein (c) is asulfonylurea herbicide.
 8. An herbicidal composition as defined in claim1 wherein R₁ and R₂ are methyl for the herbicidal 3-isoxazolidinone. 9.An herbicidal composition as defined in claim 8 wherein the3-isoxazolidinone herbicide is2-(2-chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone.
 10. Anherbicidal composition as defined in claim 1 wherein said antidotecompound is N,N-diallyl dichloroacetamide.
 11. An herbicidal compositionas defined in claim 1 wherein, in the antidotal compound, R₁ ishydrogen, C₁ -C₆ alkyl; R₂ is hydrogen or C₁ -C₆ alkyl; or R₁ and R₂taken together form a butylene, pentylene or hexylene group optionallysubstituted by one or two methyl groups; R₃ is hydrogen, C₁ -C₆ alkyl,C₂ -C₄ alkoxyalkyl, or phenyl; R₄ is hydrogen or C₁ -C₆ alkyl; and R₅and R₆ are independently hydrogen or C₁ -C₆ alkyl.
 12. An herbicidalcomposition as defined in claim 1 wherein said antidote compound is2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine.
 13. An herbicidalcomposition as defined in claim 1 wherein said antidote compound is3-(dichloroacetyl)-2,2-spirocyclohexyl oxazolidine.
 14. An herbicidalcomposition as defined in claim 1 wherein the 3-isoxazolidinoneherbicide is 2-(2-chlorophenyl) methyl-4,4-dimethyl-3-isoxazolidinoneand said antidote is N,N-diallyl dichloroacetimide.
 15. An herbicidalcomposition as defined in claim 1 wherein the 3-isoxazolidinoneherbicide is 2-(2-chlorophenyl) methyl-4,4-dimethyl-3-isoxazolidinoneand said antidote is 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine.16. An herbicidal composition as defined in claim 1 wherein the ratio of3-isoxazolidinone herbicide to antidote ranges from between about 0.1:1to about 30:1.
 17. An herbicidal composition as defined in claim 16wherein the ratio of 3-isoxazolidinone herbicide to antidote ranges frombetween about 1:1 to about 20:1.
 18. A method of controlling undesirablevegetation in the presence of a corn crop comprising applying to thelocus of said vegetation or said crop an herbicidal compositioncomprisinga) an herbicidally effective amount of a 3-isoxazolidinoneherbicide having the formula ##STR14## in which R₁ and R₂ areindependently methyl or ethyl; X is hydrogen, methyl, chlorine, bromineor fluorine; Y is chlorine, bromine or fluorine, and n is 0, 1 or 2; andb) a non-phytotoxic, antidotally effective amount, with respect to acorn crop, of an antidote compound selected from the group consisting ofN,N-diallyldichloroacetamide and compounds having the formula ##STR15##in which X is O or S and R₁ -R₆ are variously independently hydrogen,lower alkyl, alkoxyalkyl, alkylthioalkyl, or phenyl, or R₁ and R₂ takentogether form an alkylene group, and c) an herbicidally effective amountof one or more co-herbicides selected from acetamide herbicides,S-triazine herbicides, p-toluidine herbicides and sulfonylureaherbicides.
 19. A method according to claim 18 wherein (c) is anS-triazine herbicide.
 20. A method according to claim 18 wherein (c) isan acetamide herbicide.
 21. A method according to claim 20 wherein theacetamide herbicide is metolachlor.
 22. A method according to claim 20wherein the acetamide herbicide is alachlor.
 23. A method according toclaim 20 wherein the acetamide herbicide is acetochlor.
 24. Amethod-according to claim 18 wherein (c) is a sulfonylurea herbicide.25. A method according to claim 18 wherein the 3-isoxazolidinoneherbicide and the herbicide of (c) are first combined into a compositionand the composition is applied to the locus.
 26. A method according toclaim 25 in which the composition additionally includes the antidote.27. A method according to claim 18 wherein said 3-isoxazolidinoneherbicide is 2-(2-chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone.28. A method according to claim 18 wherein said antidote compound isN,N-diallyl dichloroacetamide.
 29. A method according to claim 18wherein in antidotal compound R₁ is hydrogen, C₁ -C₆ alkyl; R₂ ishydrogen or C₁ -C₆ alkyl; or R₁ and R₂ taken together form a butylene,pentylene or hexylene group optionally substituted by one or two methylgroups; R₃ is hydrogen, C₁ -C₆ alkyl, C₂ -C₄ alkoxyalkyl, or phenyl, R₄is hydrogen or C₁ -C₆ alkyl; and R₅ and R₆ are independently hydrogen orC₁ -C₆ alkyl.
 30. A method according to claim 18 wherein said antidoteis 2,2,5-trimethyl-3-(dichloroacetyl)-1-3-oxazolidine.
 31. A methodaccording to claim 18 wherein said 3-isoxazolidinone herbicide is2-(2-chlorophenyl)methyl-4,4 dimethyl 3-isoxazolidinone and saidantidote is N,N-diallyl dichloroacetamide.
 32. A method according toclaim 18 wherein said 3-isoxazolidinone herbicide is2-(2-chlorophenyl)methyl-4,4 dimethyl 3-isoxazolidinone and saidantidote is 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine.
 33. Amethod according to claim 18 wherein the ratio of 3-isoxazolidinoneherbicide to antidote ranges from about 0.1:1 to about 30:1.
 34. Amethod according to claim 18 wherein the 3-isoxazolidinone herbicide andthe antidote are first combined into a composition and the compositionis applied to the locus.
 35. A method according to claim 18 wherein the3-isoxazolidinone herbicide is applied to the locus and the antidote isseparately applied to the locus.
 36. A method according to claim 18wherein the antidote is applied as a seed treatment for the crop seedprior to planting.